Preparation of metallic derivatives of the reaction products of phosphorus sulfide and esters or amines by the use of metal carbides



Patented May 22, 1951 PREPARATION OF METALLIC DERIVA= TIVES OF THE REACTION PRODUCTS F PHOSPHORUS SULFIDE AND ES ransom m Es BY THE USE 0F METAL CARBIDES Everett -C.; Hughes, Cleveland Heights, and John D. Bartls'on, Cleveland, Ohio, assigiiors to The" Standard oil'Co'mpany, Cleveland, Ohio; a corporation of Ohio No Drawing; Appncatf gnriny 11,1946, Serial No. 682,920

1. Thisinvention'relates to a method'of pr'efial1" ing lubricants and lubricant additives suitable for use undervarious conditions;.-includihg high tei'nperatures'or high pressures; orboth, as for example; use in" an inter-hal combustion engine operating at higher temperatures and in which the lubricant is in close contact with metallic surfaces; metal'compouhds and high temperatlire gases. Lubricating oils, particularly when usedunder such conditions; are subject tobrealrdown witlilacquer deposition; sludge and acid fornfa" tion, and tend to cause corrosion of the bearing andother metals with' which they are" in con tact.

The reaction product of a phosphorus-sulfide with an organic compound to form a lubricating oil-additive has been proposed; heretofore and the'conversion of sucha reaction product to a corresponding metal derivative is also known. Suchmetal derivatives are usually formed by reaction with abase. 'Ihe'oxid'es or' hydroxides of many metals'are not sufiiciently basic, or otherwise reac-tivei so as t'o-require "superatmospheric pressure, reactants in specially prepared forms, or other undesirable reaction requirements; The objects achieved in accordance with the present inventiorrinclude the provision of an ad- 12 Claims: (Cl. 252 -3227) vantageous method-of preparing a metal deriva-- tive which-may be useful itself as alubricant, and

which when added to lubricants will markedly inhibit the very objectionable deposition of lacquer, and; at the same time, inhibitacid and sludge formation, corrosion and other types of deterioration occurring under operating condi t-ions. Other objects-will be apparent in viewof embodiments-set'forth-hereinaftcr.

In accordance with'the invention, it has been found that metal derivatives of reaction prodof phosphorus sulfides with organic compounds may be readily" prepared from the'metal carbides, specifically carbides of group II' and group III metals, e. g., calcium carbide or alumi= nu'fn carbide. invention; the sulfide-organic compound reaction producti's firstreacted Witha small amount ottvater, EXCESS watter'is removed, e. g., by'blow= iilgWVitli-IiitrOgIi, and thenthe'reaction product" i's'treatedwith'the' metal 'carbide;

The reaction of the metal carbide with the" sulfide-organic compound reaction product, which may containan added'r'eactedelement of the sulfur family, if desired, may be" carried out at any reaction temperature such as'iii the range of 300 to" about 700 F'., desirablyin the range of about-425 to seen-raw F.;- and-preferably at In a preferred embodiment of the 2 about 500' F. This reaction is usually completed in four hours or less time; dependingon' thereaction temperature, the reactivityof thecoin ponents, rate of stirring; and other" known fac tors; A diluentm'ay be used'as described hereinafter, but a diluent is not necessary. If adilu eiit was used in the sulfide-organic compound reaction step it may be carried over intothisre action step, and may be separated subsequent- 1y, if desired. From about 0.25 to about 6.0 equivalents of the metal carbide may be used per mol of the sulfide in the'sulfide organic com pound reaction product, preferably about 4.0'to about 6.0 equivalents,-- in the" case of calcium or aluminum. An equivalent is the quotient of a 11101 divided by the valence of the metal concerned. The metal carbide is'g'enerally insolu-" ble in the sulfide-organic compound reaction product, and the amount that reacts is the amount that is' no longer present in the solid phase of the reaction product.

It is beneficial to treat the primary sulfideor'ganic compound reaction product with from about 5 to about 15% by Weight thereof of water during" or befor treatment with the metal carbide. riedout; at atemperature in the range'of from about 75 to about 250 F., preferably about 200 F., if the water treatment is aseparate stepbefore thereac'tio'n with the carbide; This treatment may be conducted for aperiod of from about a few minutesto about two-hours; There'- after, any excess or uncombined water may be removed by blowing with an inert gas such as" nitrogen at atemperature of about250 F. be-- fore'treatment with the carbide; If desired the carbide maybe added first and thenwater added to the miiiture. It is'believed that the reac-" tion product obtained by reacting" water with the primary sulfide organic product, reacts directly with the metal carbide to form the metal derivative;

After the reactants have all entered into'solu tion; the" reaction is complete: The reaction mass is'then-centrifuged'or filtered to-remove wa ter' and any" trace's of oil-insoluble by product substances. If an excess of the metal compound is used, the unreacted exces's'may be separatedat this stage; If a volatile solvent was used as a diluent,- it may be'removed by'distillation. The- Treatmentwith the" water may be car-' reference to the use of the composition and the 7 properties desired in it. The alkali and'alkaline earth metals have excellent detergent characteristics. The heavier metals have surface corrosion inhibition characteristics. The preferred metals are group II and group III metals of the periodic table, such as calcium, barium and aluminum.

The derivatives containing the latter metals are not advantageously prepared by usual procedures, and the invention provides an advantageous method of providing an ash-forming calcium or aluminum-containing constituent in a lubricating oil. An ash residue is called for in certain lubricating oil specifications, as known to the art.

A plurality of metals can be used such as sodium and calcium, calcium and barium, or calcium and aluminum. If the amount of the metal is small, the final product may be a mixture of the initial reaction product and the metal derivative. In addition, mixed derivatives may be formed,

e. g., a metal carbide derivative of a partially esterified sulfide-organic compound reaction product, or a nitrogen base derivative of a sulfide-organic compound reaction product which has been partially converted to the metal derivative by treatment with a metal carbide.

The amount of the metal derivative of the sulfide-organic compound reaction product made in accordance with the invention that is to be added to an oil or greasewill depend upon the characteristics of the oil or grease and the intended use. Some oils have more of a tendency to corrode metals, or to form acids, sludges and lacquer deposits than others, and such oils require larger amounts of the additive. In general, the range is from 1 to 10%, but under some circumstances, amounts as low as .01% show a significant improvement. As to an upper limit, of course, it may be uneconomical to add more than is necessary to impart to the lubricant the desired properties. Since the derivative generally is a lubricant, it may be used alone if desired.

The sulfide-organic compound reaction products which are converted to metal compounds with a carbide in accordance with the invention are not novel. They are prepared in accordance with many heretofore proposed processes. The sulfide and the organic compound are reacted in varying proportions as is well known at various elevated reaction temperatures, and separated from a sludge if one is formed. Elemental sulfur may then be reacted with the sulfide reaction product if desired. The pentasulfide is preferred,

I though the sesquisulfide or any other sulfide or mixtures "of sulfides may be employed, Phosphorous pentasulfide is economic and readily available and for this reason was used in the i1- lustrative examples. Under suitable conditions, sulfides of arsenic or antimony may be similarly employed. The organic compound may be anywhich'reacts with a phosphorus sulfide to form phatic, alicyclic or aromatic nature.

an oil dispersible reaction product containing sulfur or sulfur and phosphorus. Generally the organic compound is of rather high molecular weight and preferably boils above the reaction temperature, i. e., above about 250 to 600 F. Those used commercially are generally of an ali- Examples are hydrocarbons such as lubricating oils, paraffins, naphthenes and olefins, olefin polymers, aromatics such as anthracene; amines such as primary and secondary amines saturated and unsaturated, and unsaturated tertiary amines; ketones such as palmitone; higher aldehydes; aromatic compounds such as benzoic and naphthoic acids; phenols such as diamyl phenol; alcohols such as lauryl alcohol; acids such as myristic, stearic and oleic acid; esters such as glyceride fats and oils, i. e. tallow and cocoanut oil, ester type waxes such as degras, beeswax, sperm oil and spermaceti, methyl stearate, cetyl butyrate etc.; oxidized petroleum products which are a mixture of acids, aldehydes, alcohols, etc., such as oxidized paraffin wax and naphthenic acid. Since these reaction products are known to the art as a general class they will not be described in more detail. Two will be selected merely as illustrative: the reaction of a phosphorus sulfide with (1) an amine and (2) hydrogenated sperm oil.

The sulfide-amine reaction product is a desirable starting material. It may be prepared by direct admixture of the reactants under reacting conditions, or by their admixture in the presence of a diluent which may or may not be subsequently removed.

The sulfide-amine reaction may be carried out under a temperature within a wide range, a temperature in the range of about to 400 F. being convenient and satisfactory. Higher temperatures up to about 600 F. or somewhat above may be used, and under such temperatures there is evolution of sulfur containing gas, for instance HzS, and the resulting primary reaction product is more oil soluble than the lower temi perature product.

The reaction time varies somewhat with the amine and the temperature and falls within the general range of from one minute to about 6 hours, desirably from about A; to about hour, and preferably about /2 hour. The reaction is usually complete in four hours or less time. The reaction time is a function of the temperature, the amount of the sulfide that is to react, the subdivision of the sulfide, rate of stirring, etc. The reaction is somewhat exothermic and on a commercial scale the heat evolved thereby may be used to maintain the temperature.

To achieve an additional improvement which results if additional sulfur is present in the additive, about 0.0 to 2.0, and preferably 0.1 to 0.7, grams atoms of sulfur per gram mol of the amine is desirable. This sulfur can be incorporated by adding elemental sulfur, preferably after the formation and cooling of the high temperature primary reaction product, and maintaining the mass at about 200 to 300 F. for about a few minutes to several hours, and preferably about one hour. Selenium and tellurium, the other members of the sulfur family, function in much the same way as sulfur in this respect, and may be incorporated similarly. The sulfur can also be added to the metal derivatives.

The reactions may be carried out in the presence or absence of air or in an atmosphere of non-deleterious gas, such as HzS or nitrogen.

cyclic ,primary or ,seconda-ry amines or derivative i primary or secondary..aminesfthereoi; allof .these *contain at l-east one amine hydrogen, which is a -hyd-rogen-attached directly to the nitrogen. The ho Q ima -b c nt o le t th desi ediubri a t sol it ch acteristi s-of .1 emrzim r su fid amine: ;or--. the final base; derivative product. *Priand se ndary:a phat ciam n w ich hzw an aliphatic ;.radical of gat aleast twelnewoarbon at m re r fe dnan w s 1 h 'momo di-octadecyl or hexadecyl amines or mixtures containing: at least one of them; are givenas illustrative. Unsaturated Ltertiary amines areeespecia-lly suitable. gAnalogous pol -yamines ;may be used. Commercial sdioctadecylamine is a :com-

mercially available amine and f -onthis reason is used in. the illustrative example.

; The aminastockwmay be amixture of different arninesof different molecular weight and degrees .of substitution and "containing 1- unsaturated or saturated-radicals. Lower primary,secondary,.or

-tertiary amines containing Y less than :twelve oar- Joonatoms ma be present.

Theyield is veryr-hig'hand appreciable amounts of oil insoluble products are not formed. Generally, .the .amount of sulfide xis ohosenso that it: will .all =react.;at..the temperature 3 selected :and

,the reaction is ,continued until it is. consumed.

\ The :othertypareactionproduct chosenasillustrative is a sulfide-organic oxygen containing compound such as an acid, alcohol ,orester of aliphatic, aromatic -or -naphthenic nature. The same general considerations apply as described heretofore. At lower temperatures, warying somewhat with .the organic oxygen containing compound, a thiophosphate is formed. When this product isdesired.the-proportions are stoichiometric for the particular wanted .thiophosphate. At higher .temperaturesof 270 to 400 E, 'depending somewhat on the organic oxygen :con- .tainin compound, amaior portionpf. the oxygen isremovedfrom the compound-to :forma reaction product high in sulfur and-lower in phosphorus .Whic'his separable froman oxygen containing The proportions preferably are such that the oxygen of the compound can be replacedby sulfur .from ,the sulfide. This reaction product, as wellas the thiophosphate, canbe reacted with added elemental sulfur.

The ,following examples of the preparation. of compositions Qinacoordance with the invention and tables of results of'tes'ts,ofdubricants-comprising some of such compositions .willservejto illustrate and point outsome advantagesbutjin no wise to limit thescope. .of the invention .as otherwise disclosed and claimed; herein.

Example 1 2(a) .800 grams of commercialdioctadecylamine (a. mixture of: about three-mans; by weight of dioctadecylamine and one -part ,of itrioctadecyl- "wereimixed :and heated to! v50.0:;F..-;and maintained at this =temperature for 3.0 minutes. :A considerable amount-:01 v:gas :which .largelygconsisted 10f HzSawasrevolved. '16 :grams "of :sulfur was added .toithereactwn;mass.iandythereactionmass'maintained at 300 for one hour, then :the product was filtered hot.

J(b) :IEOOr'grams-of the above,sulfide amine;reac- .tion-produot .(a) a-was-mixed with 33 cc. zofewater and the mixture heatedcatsabout200 F. oniasteam bath for'two': hours, with agitation. fIttwas "then blown t'withwnitrogen :for. one and one -half:hours a't 2501;F.s to 1dry1the product.

(ct) :300 :grams .of t the above water treated product 1(1)) .:and :-3-;28 grams of aluminum carbidewere mixed. andthe. mixture heated for four hours .-.at 1500 :F. with agitation. The reaction product wasfilteredrhot. 144 grams .of product was obtained as a .filtrate. It analyzed 2.01 weight percent ash.

Example 2 (a) An amine-sulfide reaction product 'was prepared inraccordancewith Example 1 (a).

(1)) A quantity of this reaction ,productwas charged to. a=reaction flask together with :12 'mols of1calcium-carbide .permolaof Piss used in-makin'g-rthe sulfide-amine reaction product. About 15 mole. of water permol of .=oalciumcarbide was slewlyvaddedzatroom temperature. Themixture was :;then gradually heated toz500 Frandrmaintainedxat :thisrztemperaturerior four hours. The producteanalyzed 510.81% .=ash.

.Emwmple 3 a) l lydrogenated sperm oil :is reacted with 20% phosphorus "sulfide at a temperature of about '300 F. This hydrogenated sperm oil is available under the trade-name of Spermofol N0. :52. it-has an iodine value of 6-7, a melting point of SO-52 C a'free fatty acid content (as oleic') of '1 .0-2-.-0-%, a saponifioation value of 135-1 38, :and about 36% of unsaponifiables. After the reaction is complete, which under the reaction conditions takes :four hours, the ma.- terial is permitted to stand, after which thebyproduct residue settles andthe reaction product is decanted; following 'this,it is filtered withthe use of a filter aid. The ,yield of the reaction product based upon hydrogenated sperm o'il raw material is (b) 360 grams of'the above sulfide-spermafol reactionproduct ,(a) was mixed with '40 grams of waterliandthe, mixture, heated at about, 200 F. on asteam bath for one and one-quarter hours, with agitation. It was'then blown with nitrogen ior three rhours at.;250

in-N270 ;grams of the above water-treated product -='(b) and 47.6 grams of calcium carbide were mixed and the mixture heated :for four hours at 500 1F. with .agitation. The reaction product was filtered -hot. .205; grams of product was ;;obta-ine d was a l-filtrate. -It analyzed 2.23 weight percentash. v

111 011181 to demonstrate 'the properties of "the metal carbide derivatives of the phosphorus -:sulfide-organic compound reaction prod-uctsin improving the characteristics of lubricating oils, a large wnumber :of representative additives .were incorporated into conventional lubricating oils. The lubr-ica ting oilscontaining these additives were ttested according to laboratory test proeduresie aluatingLin se vic stabi itmfpil as described in a paper by R. E. Burk, E. C. Hughes. W. E. Scovill and J. D. Bartleson presented at the Atlantic City meeting of the American Chemical Society in September 1941, and in another paper by the same authors presented at the New York city meeting of the American Chemical Society in September 1944, published in Industrial and Engineering Chemistry, Analytical Edition, vol. 1'7, No. 5, May 1945, pages 302-309. The latter paper also correlates the results of such laboratory tests with the so-called standardized Chevrolet Engine Test.

Essentially the laboratory test equipment consists of a vertical thermostatically heated, large glass test tube, into which is placed a piece of steel tubing of about one third its length'and of much smaller diameter. A piece of copper-lead bearing strip is suspended within and from the upper end of the steel tube by a copper pin, and 'an'air inlet is provided for admitting air into the lower end of the steel tube in such a way that in rising the air will cause the oil present to circulate. The test tube is filled with an amount of the oil to be tested which is at least sufficient to submerge the metals.

The ratios of surface active metals to the volume of oil in an internal combustion test engine are nearly quantitatively duplicated in the test equipment. In the standard test the temperature used is approximately the average temperature of the crankcase. The rate of air fiow per volume of oil is adjusted to the same as the average for a test engine in operation. Of the catalytic effects, those due to iron are the most important. They are empirically duplicated by the addition of a soluble iron salt. Those due to lead-bromide are duplicated by its addition. In the standard" test, 0.012% of iron salt is added; and in the iron tolerance test this is increased to 0.05%. The duration of the test is adjusted to that usually used in engine type tests. As is shown by the data in the papers referred to, the laboratory tests have been correlated with engine tests and the properties of the oil in an engine may be determined from the result of the laboratory tests.

The results given in the following tables were obtained from tests using:

A 160 cubic centimeter sample of the lubricant composition 70 liters of air per hour 100 square centimeters of steel surface 4.4 square centimeters of copper-lead surface 1.0 square centimeter of copper surface 0.01% by weight of lead bromide powder 0.05% soluble iron calculated as Fezoa (ferric 2- ethyl hexoate in C. P. benzene).

The iron tolerance tests were -run at 280 F. for thirty-six hours. The lacquer is deposited on the steel tube and is determined by difierence in weight of the tube after washing with chloroform and drying to constant weight. The used oil was sufficient to enable the determination of all of the usual oil tests, viz. isopentane insolubles, viscosity, acid numbers, etc.

The data in the following table shows the results obtained in testing our new additives by the tests described.

Iron tolerance tests on a conventional Mid- Continent solvent extracted lubricating oil base stock (S. A. 30) and compositions containing this oil and derivatives of phosphorus pentasulfide organic compound reaction products of the invention were run for the above described additives. -The results given in the following table are representative.

Table I Additive From Example No None 1 (c) 2 (b) 3 (0) Concentration of Additive in Per cent by weight None 1 1 l Lacquer Deposit (in milligrams) 1.2 l. O 0.8 0.2 Sludge (isopentane insoluble in milligrams) 206. 4 182. 5 37 10. 5 Acid Number 14. 5 2. 5 3. 8 0. 7 Viscosity Increase (SUS) 1, 095 610 224 44 It is evident from these data that the additives of the invention markedly improve the lubricating oil. The calcium carbide derived additive of Example 3 (c) is especially outstanding even when only 1% is added to the oil; every indicated characteristic is greatly improved thereby.'

The metal carbide derivatives prepared in accordance with the invention contain a metal or ash forming constituent. It is believed that the carbide group reacts and influences the final reaction product.

In order to prevent foaming of the oil containing a small proportion'of the additive, it is desirable in some cases to add a very small amount of tetra-amyl silicate, or an alkyl ortho carbonate, ortho formate or ortho acetate. 0.000392, of polyalkyl-silicone oil, or 0.001% of tetra-amyl silicate was found to prevent foaming upo n bubbling of air through oil containing a few percent of the additive.

The invention as claimed broadly contemplates such variations and modification of the disclosures which are apparent to one skilled in the art, except as do not come Within the following claims.

We claim:

1. In the process of preparing calciumcontaining derivatives of oil-dispersible reaction products of a phosphorus sulfide and an organic compound reactive with phosphorus sulfide and selected from the group consisting of amines and esters reactive with phosphorus sulfide, the improvement which comprises reacting said reaction product with 0.25 to 6.0 equivalents of calcium carbide per mol of the phosphorus sulfide in said reaction product at a temperature in the range of 300 to 700 F. to provide an oildispersible ash-forming calcium-containing final reaction product for use as a lubricant and as an additive for lubricants to improve their characteristics.

2. A method in accordance with claim 1 in which the phosphorus sulfide is phosphorus pentasulfide.

3. A method in accordance with claim 1 in which the organic compound is an ester type wax having at least one aliphatic radical of at least 12 carbon atoms.

4. A method in accordance with claim 1 in which the organic compound is an ester having at least one aliphatic radical and at least 12 carbon atoms.

5. A method in accordance with claim 1 which includes incorporating 0.01% to 10% of the final reaction product in a mineral lubricating oil to inhibit the deterioration thereof.

6. In the process of preparing calciumcontaining derivatives of oil-dispersible reaction products of a phosphorus sulfide and an organic compound reactive with phosphorus sulfide and selected from the group consisting of amines and esters reactive with phosphorus sulfide, the improvement which comprises reacting said reaction product with from to by weight thereof of water at a temperature in the range of 75 to 250 F., separating unreacted water therefrom and then reacting the resulting product with from 0.25 to 6.0 equivalents of calcium products of a phosphorus sulfide and an organic compound reactive with phosphorus sulfide and selected from the group consisting of amines and esters reactive with phosphorus sulfide, the improvement which comprises reacting said reaction product with water and 0.25 to 6.0 equivalents of calcium carbide per mol of phosphorus sulfide in said reaction product under conditions of pressure and temperature in the range of 300 to 700 F. to favor prompt elimination of excess unreacted water from the reaction system whereby the reaction of calcium carbide with said reaction product proceeds largely in the absence of Water to provide an oil-dispersible ash-forming calcium-containing final reaction product for use as a lubricant and as an additive for lubricants to improve their characteristics.

8. In the process of preparing calcium-containing derivatives of oil-dispersible reaction products of phosphorus sulfide and an organic amine reactive with phosphorus sulfide, the improvement which comprises reacting said reaction product with 0.25 to 6.0 equivalents of calcium carbide per mol of the phosphorus sulfide in said reaction product at a temperature in the range of 300 to 700 F. to provide an oil dispersible ashforming calcium-containing final reaction prodnot for use as a lubricant and as an additive for lubricants to improve their characteristics.

9. A method in accordance with claim 8 in which the reaction product of phosphorus sulfide and organic amine contains added reacted sulfur.

10. A method in accordance with claim 8 which includes incorporating 0.01% to 10% of the final reaction productin a mineral lubricating oil to inhibit the deterioration thereof.

11. In the process of preparing calcium-containing derivatives of oil-dispersible reaction products of phosphorus sulfide and an organic amine reactive with phosphorus sulfide, the improvement which comprises reacting said reaction product with from 5 to 15% by weight thereof of water at a temperature in the range of to 250 F., separatin unreacted water therefrom and then reacting the resulting product with from 0.25 to 6.0 equivalents of calcium carbide per mol of phosphorus sulfide in said reaction product at a temperature in the range of 300 to 700 F. to provide an oil-dispersible ash-forming calcium-containing final reaction product for use as a lubricant and as an additive for lubricants to improve their characteristics.

12. In the process of preparing calcium-containing derivatives of oil-dispersible reaction products of phosphorus sulfide and an organic amine reactive with phosphoru sulfide, the improvement which comprises reacting said reaction product with water and 0.25 to 6.0 equivalents of calcium carbide per mol of phosphorus sulfide in said reaction product under conditions of pressure and temperature in the range of 300 to 700 F. to favor prompt elimination of excess unreacted water from the reaction system whereby the reaction of calcium carbide with said reaction product proceeds largely in the absence of water to provide an oil-dispersible ash-forming calcium-containing final reaction product for use as a lubricant and as an additive for lubricants to improve their characteristics.

EVERETT C. HUGHES. JOHN D, BARTLESON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,242,260 Prutton May 20, 1941 2,316,085 Kelso Apr. 6, 1943 2,331,923 Musselman Oct. 19, 1943 2,403,474 Bartleson July 9, 1946 2,403,894 Bartleson July 9, 1946 2,419,153 Musselman Apr. 15, 1947 

1. IN THE PROCESS OF PREPARING CALCIUMCONTAINING DERIVATIVES OF OIL-DISPERSIBLE REACTION PRODUCTS OF A PHOSPHORUS SULFIDE AND AN ORGANIC COMPOUND REACTIVE WITH PHOSPHORUS SULFIDE AND SELECTED FROM THE GROUP CONSISTING OF AMINES AND ESTERS REACTIVE WITH PHOSPHORUS SULFIDE, THE IMPROVEMENT WHICH COMPRISES REACTING SAID REACTION PRODUCT WITH 0.25 TO 6.0 EQUIVALENTS OF CALCIUM CARBIDE PER MOL OF THE PHOSPHORUS SULFIDE IN SAID REACTION PRODUCT AT A TEMPERATURE IN THE RANGE OF 300 TO 700* F. TO PROVIDE AN OILDISPERSIBLE ASH-FORMING CALCIUM-CONTAINING FINAL REACTION PRODUCT FOR USE AS A LUBRICANT AND AS AN ADDITIVE FOR LUBRICANTS TO IMPROVE THEIR CHARACTERISTICS. 